膦氧化合物的还原及其在酰胺反应中的应用研究

发布时间：2018-07-26 13:31

【摘要】：有机磷化合物是工业有机合成中一类重要的有机试剂,例如三苯基膦在传统的Wittig、Mitsunobu、Staudinger、Appel反应中都作为反应的偶联剂促进反应的进行,但是在这些反应最后也都生成了一当量的副产物三苯氧膦,由于该副产物的特殊性质,给反应产物的分离带来了很大的困难,同时造成了大量的资源浪费,给环境也带来了很大的负面影响,另外还大大降低了反应的原子利用率。为了避免资源的浪费,我们探索了一条三苯氧膦直接应用的路线,该路线成功的将三苯氧膦用于促进酰胺反应的进行。一方面实现了废物利用,另一方面该合成酰胺的方法转化率高、反应条件温和、反应时间短、成本低、具有较高的原子利用率,而且通过核磁31PNMR对该反应过程进行了跟踪探讨,最后提出了合适的反应机理。另外从工业角度分析三苯氧膦的还原方法,最后经过文献调研,我们把该部分工作分为两部分。①三苯氧膦的一步还原:该方案以四甲基二硅氧烷(TMDS)为还原剂,四异丙基钛(Ti(O-iPr)4)为催化剂。并对该方案进行小型试验,从生产成本考虑,寻找最适合工业生产的反应条件。②三苯氧膦的两步还原法:以草酰氯为活化剂,将三苯氧膦活化为相应的膦氯中间体,然后在被Al/SnC12还原体系还原,其中铝粉为还原剂,二氯化锡为催化剂。并对该反应进行小型试验,从生产成本考虑,寻找最适合工业生产的反应条件。
[Abstract]:Organophosphorus compounds are important organic reagents in industrial organic synthesis, such as triphenylphosphine, which is used as a coupling agent in the traditional Wittigine Mitsunobun Staudinger appearance reaction to facilitate the reaction. However, in the end of these reactions, an equivalent by-product, triphenylphosphine oxide, was produced. Because of the special properties of the by-product, the separation of the reaction product was very difficult, and a large amount of resources were wasted at the same time. It also has a negative impact on the environment and greatly reduces the atomic utilization rate of the reaction. In order to avoid the waste of resources, we have explored a direct application route of triphenylphosphine oxide, which has been successfully used to promote the process of amide reaction. On the one hand, the waste is utilized. On the other hand, the method has the advantages of high conversion, mild reaction conditions, short reaction time, low cost and high atomic utilization ratio. Furthermore, the reaction process is tracked by nuclear magnetic 31PNMR. Finally, a suitable reaction mechanism is proposed. In addition, the reduction method of triphenylphosphine oxide is analyzed from the industrial point of view. After literature investigation, we divide this part of work into two parts, one step reduction of triphenylphosphine oxide. The scheme uses tetramethyl disiloxane (TMDS) as reducing agent. Tetraisopropyl titanium (Ti (O-iPr) 4) is used as catalyst. A small scale experiment was carried out to find out the most suitable reaction conditions for industrial production. 2. 2 triphenylphosphine oxalate was used as activator and triphenylphosphine oxide was activated to the corresponding phosphine chloride intermediate. Then it was reduced by Al/SnC12 reduction system, in which aluminum powder was used as reducing agent and tin dichloride as catalyst. A small scale test was carried out to find the most suitable reaction conditions for industrial production considering the production cost.
【学位授予单位】：上海应用技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O627.51;O621.25

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